Azines containing the 5,6-di-hydro-(1,4,2) dioxazine-3-yl group and the use thereof as fungicides

ABSTRACT

The present invention is directed to compounds of having the formula (I)                    
     in which 
     G represents a single bond or a grouping                    
      and 
     Z represents alkyl or halogenoalkyl or cycloalkyl or cycloalkylalkyl or heterocyclyl or heterocyclylalkyl or aryl or arylalkyl and 
     L 1 , L 2 , L 3  and L 4  are identical or different and independently of one another in each case represent hydrogen, halogen, cyano, nitro or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and in each case optionally substituted by 1 to 5 halogen atoms. The invention also relates to the preparation of such compounds and the use of such compounds to combat plant fungi and plant bacteria.

The invention relates to new azines, a process for their preparation andtheir use as fungicides.

It has already been disclosed that certain compounds which arestructurally similar to those described below have fungicidal properties(compare, for example, WO 95-04728, WO 97-00866). However, thefungicidal action of these compounds leaves something to be desired,especially when low amounts are applied.

The new azines of the general formula (I)

in which

G represents a single bond or a grouping

 wherein

R¹ represents in each case optionally substituted alkyl, alkenyl,alkinyl or cycloalkyl,

R represents alkyl or optionally substituted cycloalkyl having 3 to 5carbon atoms,

Z represents in each case optionally substituted alkyl, cycloalkyl,aryl, arylalkyl, heterocyclyl or heterocyclylalkyl and

L¹, L², L³ and L⁴ are identical or different and independently of oneanother in each case represent hydrogen, halogen, cyano, nitro or ineach case optionally halogen-substituted alkyl, alkoxy, alkylthio,alkylsulphinyl or alkylsulphonyl,

have now been found.

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, also when linked with heteroatoms, such as in alkoxy oralkylthio, are in each case straight-chain or branched.

Halogenoalkyl represents partly or completely halogenated alkyl. In thecase of polyhalogenated halogenoalkyl, the halogen atoms can beidentical or different. Preferred halogen atoms are fluorine andchlorine, and in particular fluorine. If the halogenoalkyl also carriesfurther substituents, the maximum possible number of halogen atoms isreduced to the free valencies remaining.

Halogen in general represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine, in particular fluorine orchlorine.

Heterocyclyl represents saturated or unsaturated and aromatic, cycliccompounds in which at least one ring member is a heteroatom, that is tosay an atom other than carbon. If the ring contains several heteroatoms,these can be identical or different. Heteroatoms are preferably oxygen,nitrogen or sulphur. If the ring contains several oxygen atoms, theseare not adjacent. If appropriate, the cyclic compounds form a polycyclicring system together with further carbocyclic or heterocyclic, fuzed-onor bridged rings. Mono- or bicyclic ring systems are preferred, inparticular mono- or bicyclic aromatic ring systems.

It has furthermore been found that the new azines of the general formula(I) are obtained by a process in which

a) ketones of the general formula (II)

 in which

G, R and Z have the abovementioned meanings,

are reacted with an aldehyde of the general formula (III)

in which

L¹, L², L³ and L⁴ have the abovementioned meanings,

and hydrazine or hydrazine hydrate,

optionally in the presence of a diluent and optionally in the presenceof a catalyst, or by a process in which

b) hydrazones of the formula (IV)

 in which

G, R and Z have the abovementioned meanings,

are reacted with an aldehyde of the general formula (III), optionally inthe presence of a diluent and optionally in the presence of a catalyst,or by a process in which

c) hydrazine derivatives of the formula (V)

 in which

L¹, L², L³ and L⁴ have the abovementioned meanings,

are reacted with a ketone of the general formula (II), optionally in thepresence of a diluent and optionally in the presence of a catalyst.

Finally, it has been found that the new azines of the general formula(I) show a very potent fungicidal action.

Where appropriate, the compounds according to the invention can be inthe form of mixtures of various possible isomeric forms, in particularof stereoisomers, such as, for example, E and Z isomers or opticalisomers. Both the E and the Z isomers, the individual enantiomers, theracemates and also any desired mixtures of these isomers are claimed.

Preferred azines of the formula (I) are those in which

G represents a single bond,

R represents alkyl having 1 to 4 carbon atoms, or cycloalkyl which has 3to 6 carbon atoms and is optionally mono- to tetrasubstituted by halogenor alkyl,

Z

represents cycloalkyl or cycloalkylalkyl which has in each case 3 to 7carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkylpart and is in each case optionally monosubstituted to tetrasubstitutedby halogen or alkyl;

represents heterocyclyl or heterocyclylalkyl which has in each case 3 to7 ring members and 1 to 4 carbon atoms in the alkyl part and isoptionally substituted by halogen or alkyl having 1 to 4 carbon atoms;

or represents aryl or arylalkyl which has in each case 6 to 10 carbonatoms in the aryl part and 1 to 4 carbon atoms in the alkyl part and isin each case optionally monosubstituted to tetrasubstituted in the arylpart in an identical or different manner, the possible substituentspreferably being chosen from the following list:

halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl,alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio,alkylsulphinyl or alkylsulphonyl having in each case 1 to 8 carbonatoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonylhaving in each case 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms;

in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,arylalkylaminocarbonyl, alkenylcarbonyl or alkinylcarbonyl having 1 to 6carbon atoms in the particular hydrocarbon chains;

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms; ineach case divalent alkylene having 3 or 4 carbon atoms, oxyalkylenehaving 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms,in each case optionally monosubstituted to tetrasubstituted in anidentical or different manner by fluorine, chlorine, oxo, methyl,trifluoromethyl or ethyl;

or a grouping

 wherein

A¹ represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkylhaving 3 to 6 carbon atoms and

A² represents hydroxyl, amino, methylamino, methyl, phenyl, benzyl,alkoxy, alkylamino or dialkylamino having 1 to 4 carbon atoms in theparticular alkyl chains and

L¹, L², L³ and L⁴ are identical or different and independently of oneanother in each case represent hydrogen, halogen, cyano, nitro or alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case1 to 6 carbon atoms and in each case optionally substituted by 1 to 5halogen atoms, preferably hydrogen or methyl, and in particularhydrogen.

Azines of the formula (I) which are likewise preferred are those inwhich

G represents a grouping

 wherein

R¹ represents hydrogen, or represents alkyl having 1 to 6 carbon atoms,alkenyl having 2 to 6 carbon atoms or alkinyl having 2 to 6 carbonatoms, in each case optionally substituted by halogen or alkoxy having 1to 4 carbon atoms, or represents cycloalkyl which has 3 to 8 carbonatoms and is optionally substituted by halogen, alkyl or alkoxy havingin each case 1 to 4 carbon atoms, or represents arylalkyl which has 1 to4 carbon atoms in the alkyl part and is optionally substituted in thearyl part, the substituents being chosen from the following list:

halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, in each casestraight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms, in each casestraight-chain or branched alkenyl, alkenyloxy or alkinyloxy having ineach case 2 to 6 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinylor halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1to 13 identical or different halogen atoms, in each case straight-chainor branched halogenoalkenyl or halogenoalkenyloxy having in each case 2to 6 carbon atoms and 1 to 11 identical or different halogen atoms, ineach case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy,hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbonatoms in the individual alkyl parts, in each case divalent alkylene ordioxyalkylene which has in each case 1 to 6 carbon atoms and is in eachcase optionally monosubstituted or polysubstituted in an identical ordifferent manner by halogen and/or straight-chain or branched alkylhaving 1 to 4 carbon atoms and/or straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms,

R represents alkyl having 1 to 4 carbon atoms, or cycloalkyl which has 3to 6 carbon atoms and is optionally monosubstituted to tetrasubstitutedby halogen or alkyl,

Z

represents alkyl or halogenoalkyl which has in each case 1 to 4 carbonatoms and is in each case optionally monosubstituted by cyano or alkoxy,

represents cycloalkyl or cycloalkylalkyl which has in each case 3 to 7carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkylpart and is in each case optionally monosubstituted to tetrasubstitutedby halogen or alkyl;

represents heterocyclyl or heterocyclylalkyl which has in each case 3 to7 ring members and 1 to 4 carbon atoms in the alkyl part and isoptionally substituted by halogen or alkyl having 1 to 4 carbon atoms;

or represents aryl or arylalkyl which has in each case 6 to 10 carbonatoms in the aryl part and 1 to 4 carbon atoms in the alkyl part and isin each case optionally monosubstituted to tetrasubstituted in anidentical or different manner in the aryl part, the possiblesubstituents preferably being chosen from the following list:

halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl,alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio,alkylsulphinyl or alkylsulphonyl having in each case 1 to 8 carbonatoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonylhaving in each case 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms;

in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,arylalkylaminocarbonyl, alkenylcarbonyl or alkinylcarbonyl having 1 to 6carbon atoms in the particular hydrocarbon chains;

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms; ineach case divalent alkylene having 3 or 4 carbon atoms, oxyalkylenehaving 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms,in each case optionally monosubstituted to tetrasubstituted in anidentical or different manner by fluorine, chlorine, oxo, methyl,trifluoromethyl or ethyl;

or a grouping

 wherein

A¹ represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkylhaving 3 to 6 carbon atoms and

A² represents hydroxyl, amino, methylamino, methyl, phenyl, benzyl,alkoxy, alkylamino or dialkylamino having 1 to 4 carbon atoms in theparticular alkyl chains and

L¹, L², L³ and L⁴ are identical or different and independently of oneanother in each case represent hydrogen, halogen, cyano, nitro or alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case1 to 6 carbon atoms and in each case optionally substituted by 1 to 5halogen atoms, preferably hydrogen or methyl, and in particularhydrogen.

Particularly preferred azines of the formula (I) are those in which

R represents methyl, ethyl, n- or i-propyl, or represents cyclopropyl,cyclobutyl or cyclopentyl, in each case optionally monosubstituted totetrasubstituted by fluorine, chlorine, methyl or ethyl, in particularrepresents methyl.

Azines of the formula (I) which are also particularly preferred arethose in which

G represents a single bond and

Z

represents cyclopentyl or cyclohexyl, in each case optionallymonosubstituted to tetrasubstituted by fluorine, chlorine, methyl orethyl;

represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl,benzopyrazolyl or furylmethyl, optionally substituted by methyl, ethyl,fluorine, chlorine or bromine;

or represents benzyl, 1-phenylethyl or 2-phenylethyl, in each caseoptionally monosubstituted to tetrasubstituted in an identical ordifferent manner, in particular substituted phenyl, the possiblesubstituents preferably being chosen from the following list:

fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio,n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl orethylsulphonyl, methylaminomethyl, dimethylaminomethyl, vinyl, allyl,2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy,2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy,2-chloro-1,1,2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino,dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl,dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,cyclopentyl, cyclohexyl, or in each case divalent propanediyl,ethyleneoxy, methylenedioxy or ethylenedioxy, in each case optionallymonosubstituted to tetrasubstituted in an identical or different mannerby fluorine, chlorine, oxo, methyl or trifluoromethyl,

or a grouping

 wherein

A¹ represents hydrogen or methyl and

A² represents hydroxyl, methoxy, ethoxy, amino, methylamino, methyl,phenyl or benzyl.

Azines of the formula (I) which are furthermore particularly preferredare those in which

G represents the grouping

 wherein

R¹ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, allyl, propargyl or but-2-en-1-yl and

Z

represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl ortrifluoromethyl, or represents cyclopentyl or cyclohexyl, in each caseoptionally monosubstituted to tetrasubstituted by fluorine, chlorine,methyl or ethyl;

represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl orfurylmethyl, optionally substituted by methyl, ethyl, fluorine, chlorineor bromine;

or represents benzyl, 1-phenylethyl or 2-phenylethyl, in each caseoptionally monosubstituted to tetrasubstituted in an identical ordifferent manner, in particular substituted phenyl, the possiblesubstituents preferably being chosen from the following list:

fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl,thiocarbmoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio,n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl orethylsulphonyl, methylaminomethyl, dimethylaminomethyl, vinyl, allyl,2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy,2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy,2-chloro-1,1,2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino,dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl,dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,cyclopentyl, cyclohexyl, or in each case divalent propanediyl,ethyleneoxy, methylenedioxy or ethylenedioxy, in each case optionallymonosubstituted to tetrasubstituted in an identical or different mannerby fluorine, chlorine, oxo, methyl or trifluoromethyl,

or a grouping

 wherein

A¹ represents hydrogen or methyl and

A² represents hydroxyl, methoxy, ethoxy, amino, methylamino, methyl,phenyl or benzyl.

Azines of the formula (I) which are also particularly preferred arethose in which

L¹, L², L³ and L⁴ are identical or different and independently of oneanother in each case represent hydrogen, fluorine, chlorine, bromine,cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, preferably hydrogen or methyl, and inparticular hydrogen.

The definitions of radicals listed above generally or stated in thepreferred ranges apply both to the end products of the formula (I) andcorrespondingly to the particular starting substances or intermediateproducts required for the preparation.

These definitions of radicals can be combined with one another asdesired, that is to say also between the stated ranges of preferredcompounds.

Formula (II) provides a general definition of the ketones required asstarting substances for carrying out process a) according to theinvention. In this formula (II), G, R and Z preferably or in particularhave those meanings which have already been mentioned as preferred or asparticularly preferred for G, R and Z in connection with the descriptionof the compounds of the formula (I) according to the invention.

The ketones of the formula (II) are known synthesis chemicals or can beprepared by customary standard methods.

Formula (III) provides a general definition of the aldehydes furthermorerequired as starting substances for carrying out process a) according tothe invention. In this formula (III), L¹, L², L³ and L⁴ preferably or inparticular have those meanings which have already been mentioned aspreferred or as particularly preferred for L¹, L², L³ and L⁴ inconnection with the description of the compounds of the formula (I)according to the invention.

The aldehydes of the formula (III) are obtained by a process in which,for example, halogenomethyl compounds of the general formula (VI)

in which

L¹, L², L³ and L⁴ have the abovementioned meanings and

Y represents halogen,

are reacted, for example, with an amine oxide, optionally in thepresence of a diluent.

The halogenomethyl compounds of the formula (VI) required for thepreparation of the aldehydes of the formula (III) are obtained, forexample, by a process in which phenoxy compounds of the general formula(VII)

in which

L¹, L², L³ and L⁴ have the abovementioned meanings and

Ar represents optionally substituted phenyl

are reacted with a carboxylic acid halide, such as, for example,acetylchloride, optionally in the presence of a diluent, such as, forexample, methylene chloride, and optionally in the presence of a Lewisacid, such as, for example, aluminium chloride.

The phenoxy compounds of the formula (VII) are known and/or can beprepared by known methods (compare, for example, WO-A 95 04 728 and DE-A195 04 625).

Formula (IV) provides a general definition of the hydrazones required asstarting substances for carrying out process b) according to theinvention. In this formula (IV), G, R and Z preferably or in particularhave those meanings which have already been mentioned as preferred or asparticularly preferred for G, R and Z in connection with the descriptionof the compounds of the formula (I) according to the invention.

The hydrazones of the formula (IV) are known or can be prepared from theketones of the formula (II) described above and hydrazine by customarystandard methods.

The hydrazones of the formula (IV-a)

in which

R, R¹ and Z have the abovementioned meanings

are new and the present invention also relates to them.

They are obtained (process d) by a process in which ketones of theformula (II-a)

in which

R, R¹ and Z have the abovementioned meanings, are reacted withhydrazine, hydrazine hydrate or one of its salts, optionally in thepresence of a diluent and optionally in the presence of a catalyst.

Formula (II-a) provides a general definition of the ketones required asstarting substances for carrying out process d) according to theinvention. In this formula (II-a), R, R¹ and Z preferably or inparticular have those meanings which have already been mentioned aspreferred or as particularly preferred for R, R¹ and Z in connectionwith the description of the compounds of the formula (1) according tothe invention.

The ketones of the formula (II-a) are known (Chem Ber. 40, 1907, 1624;Chem Ber. 38, 1905, 1919; J. Chem. Soc. 11, 1991, 1809-1818) or can beprepared by known methods.

The hydrazine or hydrazine hydrate or its salts furthermore required asa starting substance for carrying out process d) according to theinvention are known synthesis chemicals.

The aldehydes of the formula (III) furthermore required as startingsubstances for carrying out process b) according to the invention havealready been described above in the description of process a) accordingto the invention.

Formula (V) provides a general definition of the hydrazine derivativesrequired as starting substances for carrying out process c) according tothe invention. In this formula (V), L¹, L², L³ and L⁴ preferably or inparticular have those meanings which have already been mentioned aspreferred or as particularly preferred for L¹, L², L³ and L⁴ inconnection with the description of the compounds of the formula (I)according to the invention.

The hydrazine derivatives of the formula (V) are not yet known, and thepresent application also relates to them as new compounds. They areobtained (process e)) by a process in which aldehydes of the formula(III) are reacted with hydrazine, hydrazine hydrate or one of its salts,optionally in the presence of a diluent and optionally in the presenceof a catalyst.

The ketones of the formula (II) furthermore required as startingsubstances for carrying out process c) according to the invention havealready been described above in the description of process a) accordingto the invention.

Possible diluents for carrying out processes a), b), c), d) and e)according to the invention are all the inert organic solvents. Theseinclude, preferably, aliphatic, alicyclic or aromatic hydrocarbons, suchas, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,methylene chloride, chloroform, carbon tetrachloride, dichloroethane ortrichloroethane; ethers, such as diethyl ether, diisopropyl ether,methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; sulphoxides, such asdimethylsulphoxide; sulphones, such as sulpholane; or alcohols, such asmethanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol,ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethyleneglycol monomethyl ether or diethylene glycol monoethyl ether.

Processes a), b), c), d) and e) according to the invention areoptionally carried out in the presence of a catalyst. Possible catalystsare inorganic and organic acids. These include, for example, sulphuricacid, phosphoric acid, formic acid, trifluoroacetic acid,methanesulphonic acid, trifluoromethanesulphfonic acid, toluenesulphonicacid, acid ion exchangers, acid aluminas and acid silica gel.

The reaction temperatures can be varied within a substantial range incarrying out processes a), b), c), d) and e) according to the invention.In general, the reaction is carried out at temperatures from 20° C. to180° C., preferably at temperatures from 20° C. to 150° C.

For carrying out process a) according to the invention for thepreparation of the compounds of the formula (I), in general 0.5 to 2mol, preferably 0.8 to 1.5 mol, of aldehyde of the formula (III) and 0.5to 2 mol, preferably 0.8 to 1.5 mol, of hydrazine or hydrazine hydrateare employed per mole of ketone of the formula (II).

For carrying out process b) according to the invention for thepreparation of the compounds of the formula (I), in general 0.5 to 2mol, preferably 0.8 to 1.5 mol, of aldehyde of the formula (III) areemployed per mole of hydrazone of the formula (IV).

For carrying out process c) according to the invention for thepreparation of the compounds of the formula (I), in general 0.5 to 2mol, preferably 0.8 to 1.5 mol, of hydrazine derivative of the formula(V) are employed per mole of ketone of the formula (II).

Processes a), b), c), d) and e) according to the invention are ingeneral carried out under normal pressure. However, it is also possibleto carry out the processes under increased or reduced pressure—ingeneral under between 0.1 bar and 10 bar.

The reaction is carried out and the reaction products are worked up andisolated by generally customary processes (compare also the preparationexamples).

The substances according to the invention have a potent microbicidalaction and can be employed for combating undesirable microorganisms,such as fungi and bacteria, in plant protection and the preservation ofmaterials.

Fungicides can be employed in plant protection for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in plant protection for combatingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above and which may be mentioned asexamples, but not by way of limitation, are:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration by plants of the active compounds in theconcentrations necessary for combating plant diseases allows treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can be used here withparticularly good success for combating cereal diseases, such as, forexample, against Leptosphaeria, Fusarium or Puccinia species, diseasesin wine-, fruit- and vegetable-growing, such as, for example, againstPhytophtora or Plasmopara species, or rice diseases, such as, forexample, against Pyricularia species.

The active compounds according to the invention are also suitable forincreasing the harvest yield. They are moreover of low toxicity and havea good tolerance by plants.

The active compounds can be converted into the customary formulations,depending on their particular physical and/or chemical properties, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, microencapsulations in polymeric substances and in coatingcompositions for seed, as well as ULV cold mist and warm mistformulations.

These formulations are prepared in a known manner, for example by mixingthe active compounds with extenders, that is to say liquid solvents,liquefied gases under pressure and/or solid carriers, optionally usingsurface-active agents, that is to say emulsifiers and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can also be used, for example, as auxiliarysolvents. Possible liquid solvents are essentially: aromatics, such asxylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol and ethers and esters thereof, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, and water. Liquefied gaseous extenders or carriersare understood as meaning those liquids which are gaseous at normaltemperature and under normal pressure, for example aerosol propellentgases, such as halogenohydrocarbons and butane, propane, nitrogen andcarbon dioxide. Possible solid carriers are: for example, naturallyoccurring rock powders, such as kaolins, aluminas, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and synthetic rockpowders, such as highly disperse silicic acid, aluminium oxide andsilicates. Possible solid carriers for granules are: for example,crushed and fractionated natural rocks, such as calcite, marble, pumice,sepiolite and dolomite, and synthetic granules of inorganic and organicflours and granules of organic material, such as sawdust, coconutshells, maize cobs and tobacco stalks. Possible emulsifiers and/orfoam-forming agents are: for example, nonionic and anionic emulsifiers,such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates. Possible dispersingagents are: for example, lignin-sulphite waste liquors andmethylcellulose.

Adhesives, such as carboxymethylcellulose, naturally occurring andsynthetic pulverulent, granular or latex-like polymers, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and naturally occurringphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use dyestuffs, such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian blue, and organic dyestuffs,such as alizarin, azo and metal phthalocyanine dyestuffs, and tracenutrients, such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations in general comprise between 0.1 and 95 percent byweight of active compound, preferably between 0.5 and 90%.

The active compounds can be converted into the customary formulations,depending on their particular physical and/or chemical properties, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, microencapsulations in polymeric substances and in coatingcompositions for seed, as well as ULV cold and warm mist formulations.

The active compounds according to the invention can also be used, assuch or in their formulations, as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides in order thus tobroaden the action spectrum or to prevent development of resistance. Inmany cases, synergistic effects are obtained here, that is to say theactivity of the mixture is greater than the activity of the individualcomponents.

Possible mixing partners are, for example, the following compounds:

Fungicides:

aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimat, buthiobat,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, chinomethionat (quinomethionate), chlobenthiazon,chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinat,clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazol, diclofluanid, diclomezin,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimizon, fluazinam, flumetover, fluoromid,fluquinconazole, flurprimidol, flusilazol, flusulfamid, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalid,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

guazatin,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolan, isovaledione,

kasugamycin, kresoxim-methyl, copper formulations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxime, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidon, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur formulations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxid, trichlamid, tricyclazole, tridemorph,triflumizol, triforin, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamid, zineb, ziram and

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamicacid 1-isopropylester

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanoneO-(phenylmethyl)-oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol(OPP),

3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,

3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-9-carboxylic acid 2-[(phenylamino)-carbonyl]-hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,

ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

potassium bicarbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl-N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimide-amide,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran-3′-one,

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel-dimethyldithiocarbamate,kasugamycin, octhilinon, furancarboxylic acid, oxytetracycline,probenazole, streptomycin, tecloftalam, copper sulphate and other copperformulations.

Insecticides/acaricides/nematicides:

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin,

Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoro-methyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethanimideamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypennethrin, cyromazin,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfen valerate, ethiofencarb, ethion,ethofenprox, ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin, lamda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation or the active compound itself into the soil. The seed of theplants can also be treated.

When the active compounds according to the invention are employed asfungicides, the amounts applied can be varied within a substantialrange, depending on the method of application. In the treatment of partsof plants, the amounts of active compound applied are in general between0.1 and 10,000 g/hectare, preferably between 10 and 1000 g/hectare. Inthe treatment of seed, the amounts of active compound applied are ingeneral between 0.001 and 50 g per kilogram of seed, preferably between0.01 and 10 g per kilogram of seed. In the treatment of soil, theamounts of active compound applied are in general between 0.1 and 10,000g/ha, preferably between 1 and 5000 g/ha.

PREPARATION EXAMPLES Example (1)

(Process a)

0.9 g (0.0036 mol) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzaldehyde,0.69 g (0.0036 mol) of 3-trifluoromethylacetophenone, 0.18 g (0.0036mol) of hydrazine hydrate and 25 mg of 4-toluenesulphonic acid areheated under reflux in 120 ml of toluene for 18 hours using a waterseparator. After cooling, the mixture is dried over magnesium sulphateand concentrated under reduced pressure. The residue is chromatographedover silica gel with cyclohexane/ethyl acetate (5:1). 0.45 g (29% oftheory) of(5,6-dihydro-[1,4,2]dioxazin-3-yl)-(2-{[1-(3-trifluoromethylphenyl)-ethylidene]-hydrazonomethyl}-phenyl)-methanoneO-methyl oxime is obtained.

HPLC: log P=3.80

The log P values were determined in accordance with EEC Directive 79/831Annex V. A8 by HPLC (gradient method, acetonitrile/0.1% strength aqueousphosphoric acid).

Preparation of the Starting Substance

19.5 g (0.14 mol) of N-methylmorpholine N-oxide are added to a solutionof 15 g (0.056 mol) of(2-chloromethyl-phenyl)-(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methanoneO-methyl oxime in 150 ml of dimethylformamide and the mixture is stirredat 120° C. for 2 hours. After cooling, the mixture is poured into 1000ml of water and extracted three times with 200 ml of ethyl acetate eachtime. The combined organic phases are dried over magnesium sulphate andconcentrated under reduced pressure. The residue is stirred withdiisopropyl ether and the solid formed is filtered off with suction.10.5 g (76% of theory) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzaldehydeare obtained.

¹H-NMR (CDCl₃, TMS): δ3.96; 4.17-4.20; 4.53-4.56; 7.29-7.95; 9.92 ppm.

Preparation of the Precursor

61.1 g (0.775 mmol) of acetyl chloride are added to a suspension of103.4 g (0.775 mol) of anhydrous aluminium chloride in 1 l of methylenechloride in the course of 15 minutes. A solution of 105 g (0.31 mol) of(5,6-dihydro-[1,4,2]dioxazin-3-yl)-(2-o-tolyloxymethyl-phenyl)-methanoneO-methyl oxime in 500 ml of methylene chloride is added dropwise to thismixture at 20° C. under argon, the reaction mixture heating up to 30°C., and the mixture is stirred for a further 3 hours. The reactionmixture is poured onto 2 l of ice-water and extracted 3 times with 300ml of methylene chloride each time. The combined organic phases aredried over magnesium sulphate and concentrated under reduced pressure.The residue is stirred with diisopropyl ether and the solid formed isfiltered off with suction (59.1 g). The filtrate is concentrated underreduced pressure and the residue is chromatographed over silica gel withcyclohexane/ethyl acetate (3:1). A further 4 g of product are obtained.63.1 g (76% of theory) of(2-chloromethyl-phenyl)-(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methanoneO-methyl oxime are obtained in total.

¹H-NMR (CDCl₃, TMS): δ=3.99; 4.17-4.20; 4.49-4.53; 7.15-7.53 ppm.

Example (2)

(Process b)

0.4 g (0.0016 mol) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzaldehydeand 0.325 g (0.0016 mol) of 4-trifluoromethylacetophenone hydrazone areheated under reflux in 10 ml of methanol for 18 hours. After cooling,the mixture is poured into 100 ml of water and extracted three timeswith 50 ml of ethyl acetate each time. The organic phase is separatedoff, washed with 50 ml of water, dried over magnesium sulphate andconcentrated under reduced pressure. The residue is chromatographed oversilica gel with cyclohexane/ethyl acetate (3:1). 0.50 g (72% of theory)of(5,6-dihydro-[1,4,2]dioxazin-3-yl)-(2-{[1-(4-trifluoromethylphenyl)-ethylidene]-hydrazonomethyl}-phenyl)-methanoneO-methyl oxime is obtained.

HPLC: log P=3.80

Preparation of the Starting Substance

24.5 g (0.13 mol) of 4-trifluoromethylacetophenone and 26 g (0.52 mol)of hydrazine hydrate are heated under reflux in 100 ml of methanol for1.5 hours. After cooling, the mixture is poured into 800 ml of water andextracted three times with 200 ml of methylene chloride each time. Theorganic phase is separated off, dried over magnesium sulphate andconcentrated under reduced pressure. 23.5 g (89% of theory) of4-trifluoromethylacetophenone hydrazone are obtained.

Example (3)

(Process b)

1 g (0.0052 mol) of 2-hydrazono-1-phenylpropan-1-one O-methyl oxime isheated under reflux at the boiling point in 5 ml of ethanol with 1.3 g(0.0052 mol) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzaldehydeand 5 g of anhydrous magnesium sulphate for 1 hour. The reaction mixtureis poured onto water and extracted with diethyl ether, the organic phaseis dried over sodium sulphate and the solvent is distilled off in vacuo.The residue is stirred with diethyl ether and the crystals formed arefiltered off. The solid is chromatographed over silica gel withdiethylether/petroleum ether/methylene chloride (2:1:1). 0.9 g (40.8% oftheory) of crystalline2-({2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzylidene}-hydrazono)-1-phenylpropan-1-oneO-methyl oxime of melting point 136° C. is obtained.

Example (4)

(Process b)

0.5 g (0.0039 mol) of 3-hydrazono-butan-2-one O-methyl oxime is boiledunder reflux in 5 ml of ethanol with 0.96 g (0.0039 mol) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzaldehydefor 2 hours. The reaction mixture is allowed to cool slowly to 20° C.and the crystals are filtered off to give 0.9 g (64.7% of theory) of3-({2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyimino-methyl]-benzylidene}-hydrazono)-butan-2-oneO-methyl oxime.

HPLC: log P=3.17

¹H-NMR spectrum (DMSO-d6/TMS): δ=2.05 (3H); 2.14 (3H); 3.81 (3H); 3.97(3H); 407/4.08/4.10/4.12 (2H); 4.40/4.42/4.43 (2H); 7.21-7.28 (1H);7.48-7.56 (2H); 7.92-8.05 (1H); 8.10 (1H); ppm.

Preparation of the Starting Substances for Examples (3) and (4) Example(IV-a-1)

(Process d)

2.5 g (0.014 mol) of 1-phenylpropane-1,2-dione 1-(O-methyl oxime) areheated at 60° C. in 20 ml of ethanol with 1.45 g (0.029 mol) ofhydrazine hydrate for 1 hour. The reaction mixture is poured onto waterand extracted with diethyl ether, the organic phase is dried over sodiumsulphate and the solvent is distilled off in vacuo. The residue isstirred with diethyl ether and the crystals are filtered off. 1.5 g(55.6% of theory) of 2-hydrazono-1-phenylpropan-1-one O-methyl oxime ofmelting point 132° C. are obtained.

Example (IV-a-2)

(Process d)

3 g (0.026 mol) of butane-2,3-dione mono-(O-methyl oxime) are heated at60° C. in 20 ml of ethanol with 2.6 g (0.052 mol) of hydrazine hydratefor 1 hour. The reaction mixture is poured onto water and extracted withdiethyl ether, the organic phase is dried over sodium sulphate and thesolvent is distilled off in vacuo. The residue is stirred with petroleumether and the crystals are filtered off. 1 g (29.7% of theory) of3-hydrazono-butan-2-one O-methyl oxime is obtained.

HPLC: log P=0.97.

¹H-NMR spectrum (DMSO-d6/TMS): δ=1.81 (3H); 1.91 (3H); 3.83 (3H); 6.73(2H, NH₂) ppm.

The compounds of the formula (IV-b) according to the invention listed inthe following Table 1 are also prepared analogously to Examples (IV-a-1)and (IV-a-2):

TABLE 1 (IV-b)

Example Z ¹H-NMR logP (IV-a-3) Ethyl 3.82 (3H); 6.72 (2H) 1.50 (IV-a-4)iso-Propyl 3.79 (3H); 6.60 (2H) 1.88

The compounds of the formula (I-a) according to the invention listed inthe following Table 2 are also obtained analogously to Example (1), andin accordance with the general description of the preparation processaccording to the invention:

TABLE 2 (I-a)

Example G R Z logP 5 — —CH₃ 4-Ethylphenyl 3.86 6 — —CH₃3-Trifluoromethoxyphenyl 3.94 7 — —CH₃ 4-Trifluoromethoxyphenyl 8 — —CH₃4-Tolyl 3.46 9 — —CH₃ 3-Chlorophenyl 10 — —CH₃ 4-Chlorophenyl 11 — —CH₃3,4-Dichlorophenyl 12

—CH₃ i-Propyl 3.92 13

—CH₃ Ethyl 3.58 14 — —CH₃ 3-Bromophenyl 3.75 15 — —CH₃4-Difluoromethoxyphenyl 3.32 16 — —CH₃

4.38 17

—CH₃ —CH₃ 3.61 18

—CH₃ —CH₃ 4.08 19

—CH₃ —CH₃ 3.71 20

—CH₃ —CH₃ 3.20 21

—CH₃ —CH₃ 4.09 22 — —CH₃

3.22

Use Examples Example A

Phytophthora Test (Tomato)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Phytophthora infestans. The plants are thenplaced in an incubation cabin at about 20° C. and 100% relativeatmospheric humidity.

Evaluation is carried out 3 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substances according to the invention described inExamples (1), (14), (15) and (17) show a degree of action of up to 91%or more at an application amount of 100 g/hectare.

TABLE A Phytophthora test (tomato)/protective Application amount ofactive Degree of compound action Active compound in g/hectare in %according to the invention:

100 85 (17)

100 91 (15)

100 87 (14)

Example B

Plasmopara Test (Vine)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Plasmopara viticola and then remain in anincubation cabin at about 20° C. and 100% relative atmospheric humidityfor 1 day. The plants are then placed in a greenhouse at about 21° C.and about 90% relative atmospheric humidity for 5 days. The plants arethen moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substances according to the invention described inExamples (1), (4), (5), (7), (8), (12) and (13) show a degree of actionof up to 100% at an application amount of 100 g/hectare.

TABLE B Plasmopara test (vine)/protective Application amount of activeDegree of compound in action Active compound g/hectare in % according tothe invention:

100 96 (4)

100 100 (12)

100 100 (13)

100 98 (5)

100 100 (7)

100 99 (8)

Example C

Pyricularia Test (Rice)/protective

Solvent: 2.5 parts by weight of acetone

Emulsifier: 0.06 part by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe concentrate is diluted with water and the stated amount ofemulsifier to the desired concentration.

To test for protective activity, young rice plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Pyricularia oryzae. The plants are thenplaced in a greenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation is carried out 4 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substance according to the invention described inExample (1) shows a degree of action of 85% or more at an applicationamount of 750 g/hectare.

TABLE C Pyricularia test (rice)/protective Application amount of activeDegree of compound action Active compound in g/hectare in % according tothe invention:

750 90 (1)

Example D

Leptosphaeria nodorum Test (Wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are sprayed with aspore suspension of Leptosphaeria nodorum. The plants remain in anincubation cabin at 20° C. and 100% relative atmospheric humidity for 48hours.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of 80%.

Evaluation is carried out 10 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substance according to the invention described inExample (1) shows a degree of action of 95% or more at an applicationamount of 250 g/hectare.

TABLE D Leptosphaeria nodorum test (wheat)/protective Application amountof active Degree of compound in action Active compound g/hectare in %according to the invention:

250 100 (1)

Example E

Puccinia Test (Wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are sprayed with aconidia suspension of Puccinia recondita. The plants remain in anincubation cabin at 20° C. and 100% relative atmospheric humidity for 24hours.

The plants are then placed in a greenhouse at a temperature of about 20°C. and a relative atmospheric humidity of 80% in order to promote thedevelopment of rust pustules.

Evaluation is carried out 10 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substance according to the invention described inExample (1) shows a degree of action of 95% or more at an applicationamount of 250 g/hectare.

TABLE E Puccinia test (wheat)/protective Application amount of activeDegree of compound in action Active compound g/hectare in % according tothe invention:

250 100 (1)

Example F

Fusarium nivale (var. nivale) Test (Wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventarid emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are sprayed with aconidia suspension of Fusarium nivale (var. nivale).

The plants are placed in a greenhouse under translucent incubation hoodsat a temperature of about 15° C. and a relative atmospheric humidity ofabout 100%.

Evaluation is carried out 4 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substance according to the invention described inExample (1) shows a degree of action of 95% or more at an applicationamount of 250 g/hectare.

TABLE F Fusarium nivale (var. nivale) test (wheat)/protectiveApplication amount of active Degree of compound in action Activecompound g/ha in % according to the invention:

250 100 (1)

Example G

Venturia Test (Apple)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To prepare an appropriate formulation of the active compound, 1 part byweight of active compound is mixed with the stated amounts of solventand emulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theformulation of the active compound in the stated application amount.After the spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the apple scab causative organism Venturiainaequalis and then remain in an incubation cabin at about 20° C. and100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at about 21° C. and arelative atmospheric humidity of about 90%.

Evaluation is carried out 12 days after the inoculation. In thisevaluation, 0% means a degree of action which corresponds to that of thecontrol, while a degree of action of 100% means that no infestation isobserved.

In this test, the substances described in Examples (4), (5), (12), (13),(14) and (15) show a degree of action of up to 100% at an applicationamount of 10 g/hectare.

TABLE G Venturia test (apple)/protective Application amount of activeDegree of compound in action Active compound g/ha in % according to theinvention:

10 100 (4)

10 100 (12)

10 100 (13)

10 97 (5)

10 93 (15)

10 100 (14)

What is claimed is:
 1. A compound having the formula (I)

in which G represents a single bond or a grouping

 wherein R¹ represents hydrogen, or represents alkyl having 1 to 6carbon atoms, alkenyl having 2 to 6 carbon atoms or alkinyl having 2 to6 carbon atoms, in each case optionally substituted by halogen or alkoxyhaving 1 to 4 carbon atoms, or represents cycloalkyl which has 3 to 8carbon atoms and is optionally substituted by halogen, alkyl or alkoxyhaving in each case 1 to 4 carbon atoms, or represents arylalkyl whichhas 1 to 4 carbon atoms in the alkyl part and is optionally substitutedin the aryl part, the substituents being chosen from the following list:halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, in each casestraight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms, in each casestraight-chain or branched alkenyl, alkenyloxy or alkinyloxy having ineach case 2 to 6 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenalkylsulphinylor halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1to 13 identical or different halogen atoms, in each case straight-chainor branched halogenoalkenyl or halogenoalkenyloxy having in each case 2to 6 carbon atoms and 1 to 11 identical or different halogen atoms, ineach case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy,hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbonatoms in the individual alkyl parts, in each case divalent alkylene ordioxyalkylene which has in each case 1 to 6 carbon atoms and is in eachcase optionally monosubstituted or polysubstituted in an identical ordifferent manner by halogen and/or straight-chain or branched alkylhaving 1 to 4 carbon atoms and/or straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms, R represents alkyl having 1 to 4 carbon atoms,or cycloalkyl which has 3 to 6 carbon atoms and is optionally mono- totetrasubstituted by halogen or alkyl, Z represents alkyl orhalogenoalkyl which has in each case 1 to 4 carbon atoms and is in eachcase optionally monosubstituted by cyano or alkoxy; representscycloalkyl or cycloalkylalkyl which has in each case 3 to 7 carbon atomsin the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part and isin each case optionally monosubstituted to tetrasubstituted by halogenor alkyl; represents heterocyclyl or heterocyclylalkyl which has in eachcase 3 to 7 ring members and 1 to 4 carbon atoms in the alkyl part andis optionally substituted by halogen or alkyl having 1 to 4 carbonatoms, wherein said heterocyclyl or said heterocyclylalkyl is selectedfrom the group consisting of a saturated cyclic compound, an unsaturatedcyclic compound and an aromatic cyclic compound in which at least onering member is a heteroatom, wherein said heteroatom is selected fromthe group consisting of oxygen, nitrogen and sulfur with the provisothat where said cyclic compound contains more than one oxygen atom saidoxygen atoms are not adjacent, and optionally wherein said cycliccompound forms a polycyclic ring system, optionally with additionalcyclic compounds selected from the group consisting of carbocyclic andheterocyclic compounds, wherein said additional heterocyclic compoundsare as defined above, and wherein said polycyclic ring system includesrings selected from the group consisting of fused-on and bridged rings,said polycyclic ring system preferably being selected from the groupconsisting of mono-ring aromatic ring systems and bicyclic aromatic ringsystems; or represents aryl or arylalkyl which has in each case 6 to 10carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl partand is in each case optionally monosubstituted to tetrasubstituted in anidentical or different manner in the aryl part, the possiblesubstituents preferably being chosen from the following list: halogen,cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl; in each casestraight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl,alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 8 carbon atoms; in each casestraight-chain or branched alkenyl or alkenyloxy having in each case 2to 6 carbon atoms; in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinylor halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1to 13 identical or different halogen atoms; in each case straight-chainor branched halogenoalkenyl or halogenoalkenyloxy having in each case 2to 6 carbon atoms and 1 to 11 identical or different halogen atoms; ineach case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkylaminocarbonyl, diakylaminocarbonyl,arylakylaminocarbonyl, alkenylcarbonyl or alkinylcarbonyl having 1 to 6carbon atoms and in the particular hydrocarbon chains; cycloalkyl orcycloalkyloxy having in each case 3 to 6 carbon atoms; in each casedivalent alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, in each caseoptionally monosubstituted to tetrasubstituted in an identical ordifferent manner by fluorine, chlorine, oxo, methyl, trifluoromethyl orethyl; or a grouping

 wherein A¹ represents hydrogen or alkyl having 1 to 4 carbon atoms orcycloalkyl having 3 to 6 carbon atoms and A² represents hydroxyl, amino,methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino or dialkylaminohaving 1 to 4 carbon atoms in the particular alkyl chains and L¹, L², L³and L⁴ are identical or different and independently of one another ineach case represent hydrogen, halogen, cyano, nitro or in each caseoptionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinylor alkylsulphonyl having in each case 1 to 6 carbon atoms and in eachcase optionally substituted by 1 to 5 halogen atoms.
 2. The compound ofthe formula (I) according to claim 1, in which G represents a singlebond.
 3. The compound of the formula (I) according to claim 1, in whichG represents a grouping


4. The compounds of the formula (I) according to claim 1, in which Rrepresents methyl, ethyl, n- or i-propyl, or represents cyclopropyl,cyclobutyl or cyclopentyl, in each case optionally monosubstituted totetrasubstituted by fluorine, chlorine, methyl or ethyl, in particularrepresents methyl.
 5. The compounds of the formula (I) according toclaim 1, in which G represents a single bond and Z representscyclopentyl or cyclohexyl, in each case optionally monosubstituted totetrasubstituted by fluorine, chlorine, methyl or ethyl; representsthienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl, benzopyrazolyl orfurylmethyl, optionally substituted by methyl, ethyl, fluorine, chlorineor bromine; or represents benzyl, 1-phenylethyl or 2-phenylethyl, ineach case optionally monosubstituted to tetrasubstituted in an identicalor different manner, in particular substituted phenyl, the possiblesubstituents preferably being chosen from the following list: fluorine,chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio,n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl orethylsulphonyl, methylaminomethyl, dimethylaminomethyl, vinyl, allyl,2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy,2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy,2-chloro-1,1,2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino,dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl,dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,cyclopentyl, cyclohexyl, or in each case divalent propanediyl,ethyleneoxy, methylenedioxy or ethylenedioxy, in each case optionallymonosubstituted to tetrasubstituted in an identical or different mannerby fluorine, chlorine, oxo, methyl or trifluoromethyl, or a grouping

 wherein A¹ represents hydrogen or methyl and A² represents hydroxyl,methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl.
 6. Thecompounds of the formula (I) according to claim 1, in which G representsthe grouping

 and Z represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butylor trifluoromethyl, or represents cyclopentyl or cyclohexyl, in eachcase optionally monosubstituted to tetrasubstituted by fluorine,chlorine, methyl or ethyl; represents thienyl, pyridyl, furyl,thienylmethyl, pyridylmethyl or furylmethyl, optionally substituted bymethyl, ethyl, fluorine, chlorine or bromine; or represents benzyl,1-phenylethyl or 2-phenylethyl, in each case optionally monosubstitutedto tetrasubstituted in an identical or different manner, in particularsubstituted phenyl, the possible substituents preferably being chosenfrom the following list: fluorine, chlorine, bromine, cyano, nitro,amino, formyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl,n-, i-, s- or t-butyl, methoxymethyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, methylaminomethyl,dimethylaminomethyl, vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl,propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy,crotonyloxy, propargyloxy; trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, pentafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,difluoromethylthio, trifluoromethylthio, difluorochloromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino,ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl, or in each case divalentpropanediyl, ethyleneoxy, methylenedioxy or ethylenedioxy, in each caseoptionally monosubstituted to tetrasubstituted in an identical ordifferent manner by fluorine, chlorine, oxo, methyl or trifluoromethyl,or a grouping

 wherein A¹ represents hydrogen or methyl and A² represents hydroxyl,methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl.
 7. Thecompounds of the formula (I) according to claim 1, in which L¹, L², L³and L⁴ are identical or different and independently of one another ineach case represent hydrogen, fluorine, chlorine, bromine, cyano, nitro,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,n- or i-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, difluorochloromethylthio,trifluoromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, preferably hydrogen or methyl, and inparticular hydrogen.
 8. The compounds of the formula (I) according toclaim 1, in which G represents a single bond.
 9. A fungicidalcomposition, characterized by a content of at least one compound of theformula (I) according to claim
 1. 10. A method of combating fungicomprising the step of applying a fungicidally effective amount of acompound of the formula (I) according to claim 1 to a member selectedfrom the group consisting of said fungi, an environment of said fungi,and combinations thereof.
 11. A process for the preparation of compoundsof the formula (I) as defined in claim 1 comprising reacting a) ketonesof the formula (II)

 in which G, R and Z have the meanings given in claim 1, with analdehyde of the formula (III)

in which L¹, L², L³ and L⁴ have the meanings given in claim 1, andhydrazine or hydrazine hydrate, optionally in the presence of a diluentand optionally in the presence of a catalyst, or reacting b) hydrazonesof the formula (IV)

 in which G, R and Z have the meanings given in claim 1, are reactedwith an aldehyde of the formula (III), optionally in the presence of adiluent and optionally in the presence of a catalyst, or reacting c)hydrazine derivatives of the formula (V)

 in which L¹, L², L³ and L⁴ have the meanings given in claim 1, with aketone of the formula (II), optionally in the presence of a diluent andoptionally in the presence of a catalyst.
 12. A compound having theformula (III)

in which L¹, L², L³ and L⁴ have the meanings given in claim
 1. 13. Acompound having the formula (I) according to claim 1, in which Grepresents a grouping

 wherein R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- ors-butyl, allyl, propargyl or but-2-en-1-yl.
 14. The compounds of claim1, wherein L¹, L², L³ and L⁴ are identical or differently andindependently of one another in each case represent hydrogen or methyl.